Gem-borylsilylalkanes　are　versatile　intermediates　in　organic　synthesis,　and　the　traditional　synthesis　methods　have　mainly　focused　on　metal　reagents,　the　insertion　reactions　of　diazo　compounds,　and　hydrosilylation/hydroborylation　reactions　of　unsaturated　bonds.　Herein,　a　novel,　efficient　gem-borylsilylalkanes　synthesis　via　a　radical　approach　is　reported.　This　method　introduced　a　β-gem-borylsilyl　NHPI　ester　as　the　precursor　of　the　β-borylsilyl　radical　that,　coupling　with　radical　acceptors　under　photo　conditions,　and　the　corresponding　gem-borylsilylalkanes　bearing　unsaturated　bonds,　facilitate　subsequent　transformations.　©　2024　American　Chemical　Society.